CN109433120B - Nanofiber gel material with pollutant adsorption, catalysis and fluorescence tracking synergistic functions and preparation method thereof - Google Patents

Nanofiber gel material with pollutant adsorption, catalysis and fluorescence tracking synergistic functions and preparation method thereof Download PDF

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CN109433120B
CN109433120B CN201811280989.0A CN201811280989A CN109433120B CN 109433120 B CN109433120 B CN 109433120B CN 201811280989 A CN201811280989 A CN 201811280989A CN 109433120 B CN109433120 B CN 109433120B
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CN109433120A (en
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刘轲
王栋
刘迎
万雨彩
刘琼珍
王雯雯
李沐芳
蒋海青
鲁振坦
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Wuhan Textile University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B01J13/0065—Preparation of gels containing an organic phase
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products

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Abstract

The invention discloses a nanofiber gel material with the functions of pollutant adsorption, catalysis and fluorescence tracking and a preparation method thereof, and belongs to the technical field of textile materials. The nanofiber gel material is formed by mutually intertwining particle-doped metal organic framework nanofibers and thermoplastic polymer nanofibers in a three-dimensional space through hydrogen bond acting force; the preparation method comprises the following steps of firstly preparing metal organic framework nano fibers doped with internal metal particles, then dispersing the thermoplastic polymer nano fibers prepared by a melt blending phase separation method into a mixed solvent of an organic solvent and water to form a suspension, then coating the suspension on a substrate, and obtaining the nano fiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking by a freeze drying technology. The preparation process is simple, and the prepared material has multiple functions.

Description

Nanofiber gel material with pollutant adsorption, catalysis and fluorescence tracking synergistic functions and preparation method thereof
Technical Field
The invention relates to a nanofiber material, belongs to the technical field of textile materials, and particularly relates to a nanofiber gel material with the functions of pollutant adsorption, catalysis and fluorescence tracking and a preparation method thereof.
Background
The gel material has a three-dimensional through network structure and has wide application prospects in aspects of substance adsorption, storage, heat insulation, catalytic separation and the like. The skeleton structure of the material is a main carrier for exerting the performance of the gel, and the realization of function diversification and performance improvement through structural morphology regulation becomes a main way for the development of the gel material. The nano-fiber has a large length-diameter ratio, and the specific surface area of the gel material prepared from the nano-fiber can be remarkably improved, so that the performance of the material is enhanced. In recent years, nanofiber gel materials have become a global focus of research.
The metal organic framework material is a porous organic complex combining inorganic and organic, can form different framework pore structures, and the stable pore structure can load metal or metal oxide particles with smaller sizes, thereby showing more excellent performances such as selective adsorption, catalysis, sensing and the like. However, the nano-scale metal organic framework materials prepared in large scale at present are generally granular, have poor processability, and are difficult to be compounded with nano fibers to prepare nano fiber gel materials. Although the metal organic framework nano particles can be fixed on the surface of the fiber by adopting an in-situ growth method, the method has complex process and high energy consumption, and the application of the metal organic framework material in a gel system is limited. Although the metal organic framework material is prepared into the nano-fiber at present, the preparation process is relatively complex to operate.
Disclosure of Invention
In order to solve the technical problems, the invention provides a nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking and a preparation method thereof. The nanofiber gel material is coated with the functional metal nanoparticles in the fibrous metal organic framework and mutually interpenetrated with the thermoplastic polymer nanofibers, so that the nanofiber gel material can be subjected to heterogeneous catalysis in water pollutants, and meanwhile, the loss of the functional particles is further prevented due to the combination of the metal organic framework and the nanofibers, so that the secondary pollution of water is prevented.
In order to achieve the purpose, the invention discloses a nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking, which is formed by mutually intertwining metal organic framework nanofibers and thermoplastic polymer nanofibers in a three-dimensional space through hydrogen bond acting force, wherein the metal organic framework nanofibers are doped with nano metal particles, and the mass percentage of each nanofiber is as follows:
thermoplastic polymer nanofibers: 20 to 99 percent;
metal organic framework nanofiber: 1 to 80 percent.
Preferably, the mass percentage of the nano metal particles in the metal organic framework nano fiber is 1% -10% of that of the metal organic framework nano fiber, and the reasonably adsorbed nano metal particles are beneficial to realizing the functions of catalysis, fluorescence tracking and the like.
Further, the fiber diameter of the metal organic framework nanofiber is 20-1000 nm, and the fiber length is 5-100 μm; the particle size of the nano metal particles is 1-10 nm.
The metal organic framework nanofiber is prepared by combining rare earth metal salt and an organic ligand, wherein the rare earth metal salt is an inorganic compound consisting of at least one element of Eu (europium), Ga (gallium), Tb (terbium), Sm (samarium), Yb (ytterbium) and Ru (ruthenium), the organic ligand is polybasic organic carboxylic acid containing a benzene ring structure, and the polybasic organic carboxylic acid containing the benzene ring structure is at least one of trimesic acid, 1,3, 5-tri (4-carboxyphenyl) benzene or nitrilotriacetic acid.
Further, the nano metal particles are at least one of silver, gold, platinum, copper, iron, nickel or palladium.
Further, the thermoplastic polymer nanofiber is a nanofiber with the fiber diameter of 50-500 nm, which is prepared from a thermoplastic polymer by a melt blending phase separation method; the thermoplastic polymer is one of polyamide and ethylene vinyl alcohol copolymer.
In order to better realize the aim of the invention, the invention also discloses a preparation method of the nanofiber gel material with the pollutant adsorption, catalysis and fluorescence tracking synergistic functions, which comprises the following preparation steps:
1) preparing metal organic framework nano fibers: uniformly mixing a rare earth metal salt solution and an organic ligand solution to obtain a mixed stock solution, placing the mixed stock solution in a water bath shaking table, uniformly oscillating to obtain nano fibers, placing the nano fibers in a precursor salt solution of nano metal particles, continuing oscillation of the water bath shaking table, performing suction filtration and washing to obtain metal organic framework nano fibers with nano metal cations adsorbed on the surfaces and in the metal organic framework nano fibers, and performing reduction treatment to prepare the metal organic framework nano fibers with the nano metal particles doped on the surfaces and in the metal organic framework nano fibers;
2) preparing thermoplastic polymer nanofibers;
3) preparing a suspension: dispersing the metal organic framework nano-fiber obtained in the step 1), the thermoplastic polymer nano-fiber obtained in the step 2) and a chemical modifier in a mixed solvent to form a uniform suspension;
4) preparing an aerogel material: coating the suspension obtained in the step 3) on the surface of a base material, placing, and preparing the nanofiber gel material by using a freeze-drying technology.
Preferably, the suspension obtained in the step 3) is coated on the surface of the base material and is preserved for 1-120 min at a constant temperature of 20-50 ℃.
Further, in the step 1), the volume ratio of the rare earth metal salt solution to the organic ligand solution is (1-3) to 1, and the water temperature of the water bath shaking table is 20-50 ℃.
Further, the rare earth metal salt solution is a solution prepared by dissolving at least one inorganic compound of Eu, Ga, Tb, Sm, Ya or Ru into a mixed solution of an organic solvent and water to obtain a concentration of 0.01-0.5 mol/L, and the volume ratio of the organic solvent to the water is (1-4): 1, the organic solvent is one of ethanol, methanol or DMF.
Further, the organic ligand solution is a solution prepared by dissolving at least one of trimesic acid, 1,3, 5-tris (4-carboxyphenyl) benzene or nitrilotriacetic acid in a mixed solution of an organic solvent and water to obtain a concentration of 0.01-0.5 mol/L, and the volume ratio of the organic solvent to the water is (2-8): 1, the organic solvent is one of ethanol, methanol or DMF.
Further, in step 1), the precursor salt solution of the nano-metal particles is an aqueous solution of an inorganic compound of one element of silver, gold, platinum, copper, iron, nickel or palladium.
Further, in the step 1), the reducing agent adopted in the reduction reaction is one of ethanol, sodium borohydride or hydrazine hydrate.
Further, in step 3), the mixed solvent is a mixed solution of water and an organic solvent, and the organic solvent is one of ethanol, methanol or DMF.
Further, in the step 4), the freeze drying is carried out at the temperature of-80 to-10 ℃, the freezing time is 4 to 6 hours, and the drying time is 24 to 72 hours.
Preferably, the aerogel material is prepared by a freeze-drying process.
Most preferably, the base material is one of woven cloth, non-woven cloth and smooth organic polymer film material.
The principle that the nanofiber gel prepared by the method has the synergistic functions of adsorption, catalysis and fluorescence tracking is described as follows:
(1) the gel material designed by the application has high porosity and specific surface area, is beneficial to the transportation and adsorption of target molecules, and the target molecules screened by the framework pore diameter of the metal organic framework nano fibers are adsorbed inside the metal organic framework nano fibers;
(2) the nanofiber gel designed by the application has a catalytic function, and is characterized in that electrons are easier to obtain a reduction product or electrons are easier to lose to obtain an oxidation product under the catalytic action of high-activity nano metal particles loaded in the metal organic framework nanofiber by adsorbed target molecules;
(3) the nanofiber gel designed by the application has a fluorescence tracking synergistic function, and is characterized in that the interaction between an adsorbed target molecule and a lanthanide metal center and an organic ligand in a metal organic framework influences the fluorescence luminous performance of a metal organic framework material, a spectrum with a specific wavelength and specific strength is emitted, and the interaction between a product generated after catalytic reaction and the lanthanide metal center and the organic ligand of the metal organic framework is changed, so that a fluorescence quenching phenomenon is generated, and the purpose of changing a fluorescence sensing target molecule into a product molecule is achieved.
The beneficial effects of the invention are mainly embodied in the following aspects:
1. the preparation method designed by the invention is to prepare the metal organic framework material into a nano fiber shape, the nano fiber shape material and the thermoplastic polymer nano fiber are mutually entangled in space, and nano metal particles are doped in the nano fiber shape material to prepare the nano fiber gel material;
2. the carbonyl in the organic ligand in the metal organic framework nanofiber and the hydroxyl in the ethylene vinyl alcohol copolymer nanofiber or the amide in the polyamide nanofiber can mutually form a hydrogen bond, so that the strength of the nanofiber gel material is improved on the basis of mechanical external force between molecules, and the structural stability is good;
3. the invention relates to a method for preparing metal organic framework nano-fiber doped with nano-metal particles by adsorbing nano-metal cations (the cations adsorbed on the surface are removed by a washing process) in the internal pores of the metal organic framework nano-fiber and reducing in situ, and the protection of the nano-metal particles and the uniformity of the size of the nano-metal particles are realized by the size limitation of the pores of the metal organic framework nano-fiber;
4. the nanofiber gel material designed by the invention has an excellent function of adsorbing target molecules by virtue of a larger specific surface area of the metal organic framework nanofiber exposed outside the thermoplastic polymer nanofiber, and simultaneously not only is the prepared nanofiber gel material provided with a catalytic property, but also the excellent fluorescence sensing property of the metal organic framework nanofiber is endowed by virtue of the high activity of the nano metal particles inside the metal organic framework nanofiber and the multiple luminescence properties of the material (realized by the interaction of rare earth metal, organic ligand and nano metal particles).
Drawings
FIG. 1 is a scanning electron microscope image of a gel material prepared according to the present invention;
FIG. 2 is a schematic illustration of the action of forces between fibers within the gel material of FIG. 1;
FIG. 3 is a schematic view of the action of force between some of the fibers of FIG. 2;
FIG. 4 is a schematic view of the action of force between some of the fibers of FIG. 2;
FIG. 5 is a schematic view of the action of force between some of the fibers of FIG. 2;
wherein, the reference numbers in fig. 1 to 5 are as follows:
metal organic framework nano-fiber a, thermoplastic polymer nano-fiber b (wherein, polyamide nano-fiber b-1, ethylene vinyl alcohol copolymer nano-fiber b-2) and nano-metal particles c;
the method comprises the following steps of 1 acting force of hydrogen bonds among thermoplastic polymer nanofibers, 2 acting force of hydrogen bonds among metal organic framework nanofibers, 3 acting force of hydrogen bonds between the metal organic framework nanofibers and the thermoplastic polymer nanofibers, 4 acting force of mechanical entanglement and hydrogen bonds between the metal organic framework nanofibers and the thermoplastic polymer nanofibers, and 5 acting force of mechanical entanglement and hydrogen bonds among the thermoplastic polymer nanofibers.
Detailed Description
In order to better explain the invention, the following further illustrate the main content of the invention in connection with specific examples, but the content of the invention is not limited to the following examples.
Example 1
Preparing 0.01mol/L europium nitrate solution, wherein the solvent composition is alcohol-water mass ratio of 1:1 (preferably ethanol). 0.01mol/L trimesic acid organic ligand solution is prepared, wherein the mass ratio of alcohol to water in the solvent is 2:1 (preferably ethanol). Blending the prepared europium nitrate solution of metal salt and organic ligand solution of trimesic acid according to the volume ratio of 1:1, then placing the mixture in a water bath shaking table at 20 ℃, uniformly shaking the mixture for 12 hours to prepare metal organic framework fibers, placing the metal organic framework fibers in silver nitrate solution for adsorbing the metal organic framework fibers for 30 minutes, taking out the metal organic framework fibers, performing suction filtration and washing, and then placing the metal organic framework fibers in ethanol for reacting for 10 hours to prepare Eu- (BTC) MOFS nano fibers doped with nano metal silver particles;
dispersing thermoplastic nano-fiber (polyamide) and the Eu (BTC) MOFS nano-fiber doped with nano-metal silver particles in alcohol water to form a suspension (preferably a mixed solution of ethanol and water), wherein the Eu (BTC) MOFS nano-fiber doped with nano-metal silver particles in the suspension is 1% by mass, and the Eu (BTC) MOFS nano-fiber doped with nano-metal silver particles in the suspension and the thermoplastic nano-fiber are in a mass ratio of 0.1: 1.
The suspension is coated on a base material (non-woven fabric), and is frozen for 4 hours at the temperature of-10 ℃ by a freeze drying technology, and is dried for 24 hours to obtain the nanofiber gel material with the synergistic function of pollutant adsorption-catalysis-fluorescence tracking.
As shown in fig. 1, the gel material prepared in this example is formed by mutually intertwining metal organic framework nanofibers a and thermoplastic polymer nanofibers b in a three-dimensional space; and the inside of the metal organic framework nano fiber a is doped with nano metal particles c.
As shown in fig. 2, the acting force between the metal organic framework nanofiber a and the thermoplastic polymer nanofiber b includes hydrogen bond acting force or mechanical force of mutual entanglement, including hydrogen bond acting force 1 between thermoplastic polymer nanofibers (hydrogen bond acting force between polyamide nanofibers or hydrogen bond acting force between ethylene vinyl alcohol copolymer nanofibers), hydrogen bond acting force 2 between metal organic framework nanofibers, hydrogen bond acting force 3 between metal organic framework nanofibers and thermoplastic polymer nanofibers (including hydrogen bond acting force between metal organic framework nanofibers and polyamide nanofibers or hydrogen bond acting force between metal organic framework nanofibers and ethylene vinyl alcohol copolymer nanofibers), the combined action force of mechanical entanglement and hydrogen bonds between the metal organic framework nano-fibers and the thermoplastic polymer nano-fibers is 4, and the combined action force of mechanical entanglement and hydrogen bonds between the thermoplastic polymer nano-fibers is 5.
Further, as can be seen from FIG. 3, there are hydrogen bonding force 1 between the polyamide nanofibers b-1 and hydrogen bonding force 1 between the ethylene vinyl alcohol copolymer nanofibers b-2;
as shown in fig. 4, hydrogen bonding force 2 exists between the metal organic framework nanofibers a;
as shown in FIG. 5, there is a hydrogen bonding force 3 between the polyamide nanofiber b-1 and the metal organic framework nanofiber a, and there is also a hydrogen bonding force 3 between the ethylene vinyl alcohol copolymer nanofiber b-2 and the metal organic framework nanofiber a.
The combination of all acting forces strengthens the connection between the thermoplastic polymer nano-fiber and the linear metal organic framework nano-fiber, so that the prepared membrane material or aerogel material can stably exist in space.
The structure of the membrane material or aerogel material prepared in the following examples is the same as that of the present example, and therefore, the description thereof is omitted.
Example 2
Preparing 0.1mol/L europium nitrate solution, wherein the solvent composition is alcohol-water mass ratio of 1:1 (methanol is preferred). Preparing 0.1 mol/L1, 3, 5-tri (4-carboxyphenyl) benzene (BTBC) organic ligand solution, wherein the solvent composition is that the mass ratio of alcohol to water is 2:1 (methanol is preferred). Mixing the prepared europium nitrate solution of metal salt and 1,3, 5-tri (4-carboxyphenyl) benzene (BTBC) organic ligand solution according to the volume ratio of 1:1, then placing the mixture in a water bath shaking table at the temperature of 20 ℃, uniformly shaking the mixture for 12 hours to prepare Eu (BTBC) MOFS nano fiber, placing the Eu (BTBC) MOFS nano fiber in copper sulfate solution for adsorption for 30 minutes, taking out the Eu (BTBC) MOFS nano fiber, carrying out suction filtration and washing, and then placing the Eu (BTBC) MOFS nano fiber in NaHCO4Reacting for 5h to prepare Eu (BTBC) MOFS nano-fiber doped with nano-metal copper particles;
dispersing thermoplastic nanofibers (polyamide) and the Eu (BTBC) MOFS nanofibers doped with nano-metal copper particles in the interior in alcohol water to form a suspension (preferably a mixed solution of methanol and water), wherein the Eu (BTBC) MOFS nanofibers doped with nano-metal copper particles in the interior are 1% by mass, and the Eu (BTBC) MOFS nanofibers doped with nano-metal copper particles in the interior and the thermoplastic nanofibers are in a mass ratio of 0.1: 1.
The suspension is coated on a base material (non-woven fabric), and is frozen for 4 hours at the temperature of-10 ℃ by a freeze drying technology, and is dried for 24 hours to obtain the nanofiber gel material with the synergistic function of pollutant adsorption-catalysis-fluorescence tracking.
Example 3
Preparing 0.15mol/L europium nitrate solution, wherein the solvent composition is that the mass ratio of alcohol to water is 1: 1. Preparing 0.15mol/L nitrilotriacetic acid (NTA) organic ligand solution, wherein the mass ratio of alcohol to water is 2: 1. Mixing the prepared europium nitrate solution of metal salt and nitrilotriacetic acid (NTA) organic ligand solution according to the volume ratio of 1:1, then placing the mixture in a water bath shaker at 20 ℃, uniformly shaking the mixture for 12h to prepare Eu (NTA) MOFs nano-fiber, placing the Eu (NTA) MOFs nano-fiber in a palladium chloride solution for adsorption for 30min, taking out the nano-fiber, performing suction filtration and washing, and then placing the nano-fiber in NaHPO4Reacting for 5h to prepare Eu (NTA) MOFs nano-fiber doped with nano-metal palladium particles;
dispersing thermoplastic nano-fibers (polyamide) and the Eu (NTA) MOFs nano-fibers doped with nano-metal palladium particles in alcohol water to form a suspension (preferably a mixed solution of methanol and water), wherein the Eu (NTA) MOFs nano-fibers doped with nano-metal palladium particles in the interior are 1 mass percent, and the Eu (NTA) MOFs nano-fibers doped with nano-metal palladium particles in the interior and the thermoplastic nano-fibers are in a mass ratio of 0.1: 1.
The suspension is coated on a base material (non-woven fabric), and is frozen for 4 hours at the temperature of-10 ℃ by a freeze drying technology, and is dried for 24 hours to obtain the nanofiber gel material with the synergistic function of pollutant adsorption-catalysis-fluorescence tracking.
Example 4
Preparing 0.2mol/L europium nitrate solution, wherein the solvent composition is that the mass ratio of alcohol to water is 1: 1. 0.2mol/L trimesic acid organic ligand solution is prepared, wherein the solvent composition is that the mass ratio of alcohol to water is 2: 1. Blending the prepared europium nitrate solution of metal salt and organic ligand solution of trimesic acid according to the volume ratio of 1:1, then placing the mixture in a water bath shaking table at the temperature of 30 ℃, uniformly shaking the mixture for 12 hours to prepare Eu (BTC) MOFs nano fiber, placing the Eu (BTC) MOFs nano fiber in ferric chloride solution for adsorption for 30 minutes, taking out the solution, performing suction filtration and washing, and then placing the solution into NaHPO4Reacting for 5h to prepare Eu (BTC) MOFs nano-fiber doped with nano-metallic iron particles;
dispersing thermoplastic nanofibers (polyamide) and the Eu- (BTC) MOFs nanofibers doped with nano metallic iron particles in alcohol water to form a suspension (preferably a mixed solution of methanol and water), wherein the Eu- (BTC) MOFs nanofibers doped with nano metallic iron particles in the suspension are 1% by mass, and the Eu- (BTC) MOFs nanofibers doped with nano metallic iron particles in the suspension and the thermoplastic nanofibers are in a mass ratio of 0.1: 1.
The suspension is coated on a base material (non-woven fabric), and is frozen for 4 hours at the temperature of-10 ℃ by a freeze drying technology, and is dried for 24 hours to obtain the nanofiber gel material with the synergistic function of pollutant adsorption-catalysis-fluorescence tracking.
Example 5
Preparing 0.3mol/L europium nitrate solution, wherein the solvent composition is that the mass ratio of alcohol to water is 1: 1. 0.3mol/L trimesic acid organic ligand solution is prepared, wherein the solvent composition is that the mass ratio of alcohol to water is 2: 1. Blending the prepared europium nitrate solution of metal salt and organic ligand solution of trimesic acid according to the volume ratio of 1:1, then placing the mixture in a water bath shaking table at 35 ℃, uniformly shaking the mixture for 12 hours to prepare Eu (BTC) MOFs nanofiber, placing the Eu (BTC) MOFs nanofiber in nickel sulfate hexahydrate solution for adsorption for 30 minutes, taking out the Eu (BTC) MOFs nanofiber, performing suction filtration and washing, and then placing the Eu (BTC) MOFs nanofiber in hydrazine hydrate for reaction for 5 hours to prepare Eu (BTC) MOFs nanofiber with surface and inside doped with nano metal nickel particles;
dispersing thermoplastic nanofibers (polyamide) and the Eu- (BTC) MOFs nanofibers doped with nano metal nickel particles in the interior in alcohol water to form a suspension (preferably a mixed solution of methanol and water), wherein the Eu- (BTC) MOFs nanofibers doped with nano metal nickel particles in the interior are 1% by mass, and the Eu- (BTC) MOFs nanofibers doped with nano metal nickel particles in the interior and the thermoplastic nanofibers are in a mass ratio of 0.1: 1.
The suspension is coated on a base material (woven cloth), and is frozen for 4 hours at the temperature of minus 10 ℃ and dried for 24 hours by a freeze-drying technology to obtain the nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking.
Example 6
Preparing 0.4mol/L europium nitrate solution, wherein the solvent composition is that the mass ratio of alcohol to water is 1: 1. 0.4mol/L trimesic acid organic ligand solution is prepared, wherein the solvent composition is that the mass ratio of alcohol to water is 2: 1. Blending the prepared europium nitrate solution of metal salt and organic ligand solution of trimesic acid according to the volume ratio of 1:1, then placing the mixture in a water bath shaking table at 40 ℃, uniformly shaking the mixture for 12 hours to prepare Eu (BTC) MOFs nano fiber, placing the Eu (BTC) MOFs nano fiber in chloroplatinic acid solution for adsorption for 30 minutes, taking out the solution, performing suction filtration and washing, and then placing the solution into NaHPO4Reacting for 5 hours to prepare Eu (BTC) MOFs nano-fibers with the surfaces and the interiors both doped with nano-metal platinum particles;
dispersing thermoplastic nano-fibers (polyamide) and the Eu- (BTC) MOFs nano-fibers doped with nano-metal platinum particles in alcohol water to form a suspension (preferably a mixed solution of methanol and water), wherein the Eu- (BTC) MOFs nano-fibers doped with nano-metal platinum particles in the interior are 1% by mass, and the Eu- (BTC) MOFs nano-fibers and the thermoplastic nano-fibers both doped with nano-metal platinum particles in the interior are in a mass ratio of 0.1: 1.
The suspension is coated on a base material (woven cloth), and is frozen for 4 hours at the temperature of minus 20 ℃ by a freeze drying technology, and is dried for 24 hours to obtain the nanofiber gel material with the synergistic function of pollutant adsorption, catalysis and fluorescence tracking.
Example 7
Preparing 0.5mol/L europium nitrate solution, wherein the solvent composition is that the mass ratio of alcohol to water is 1: 1. 0.5mol/L trimesic acid organic ligand solution is prepared, wherein the solvent composition is that the mass ratio of alcohol to water is 2: 1. Blending the prepared europium nitrate solution of metal salt and organic ligand solution of trimesic acid according to the volume ratio of 1:1, then placing the mixture in a water bath shaking table at 50 ℃, uniformly shaking the mixture for 12 hours to prepare Eu (BTC) MOFs nano fiber, placing the Eu (BTC) MOFs nano fiber in silver nitrate solution for adsorption for 30 minutes, taking out the solution, performing suction filtration and washing, and then placing the solution into NaHPO4Reacting for 5 hours to prepare Eu (BTC) MOFs nano-fiber with nano-metal silver particles doped inside;
dispersing thermoplastic nano-fibers (polyamide) and the Eu- (BTC) MOFs nano-fibers doped with nano-metallic silver particles in alcohol water to form a suspension (preferably a mixed solution of methanol and water), wherein the Eu- (BTC) MOFs nano-fibers doped with nano-metallic silver particles in the suspension are 1 mass percent, and the Eu- (BTC) MOFs nano-fibers doped with nano-metallic silver particles in the suspension and the thermoplastic nano-fibers are in a mass ratio of 0.1: 1.
The suspension is coated on a base material (woven cloth), and is frozen for 4 hours at the temperature of minus 30 ℃ and dried for 24 hours by a freeze-drying technology to obtain the nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking.
Example 8
Preparing 0.01mol/L europium nitrate solution, wherein the solvent composition is that the mass ratio of alcohol to water is 1: 1. 0.01mol/L trimesic acid organic ligand solution is prepared, wherein the solvent composition is that the mass ratio of alcohol to water is 2: 1. Blending the prepared europium nitrate solution of metal salt and organic ligand solution of trimesic acid according to the volume ratio of 2:1, then placing the mixture in a water bath shaking table at the temperature of 20 ℃, uniformly shaking the mixture for 12 hours to prepare Eu (BTC) MOFs nano fiber, placing the Eu (BTC) MOFs nano fiber in silver nitrate solution for adsorption for 30 minutes, taking out the solution, performing suction filtration and washing, and then placing the solution into NaHPO4Reacting for 5 hours to prepare Eu (BTC) MOFs nano-fibers with the surfaces and the interiors both doped with nano-metal silver particles;
dispersing thermoplastic nano-fibers (polyamide) and the Eu- (BTC) MOFs nano-fibers doped with nano-metallic silver particles in alcohol water to form a suspension (preferably a mixed solution of methanol and water), wherein the Eu- (BTC) MOFs nano-fibers doped with nano-metallic silver particles in the suspension are 1 mass percent, and the Eu- (BTC) MOFs nano-fibers doped with nano-metallic silver particles in the suspension and the thermoplastic nano-fibers are in a mass ratio of 0.1: 1.
The suspension is coated on a base material (woven cloth), and is frozen for 4 hours at the temperature of 50 ℃ below zero by a freeze-drying technology, and is dried for 24 hours to obtain the nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking.
Example 9
Preparing 0.1mol/L europium nitrate solution, whereinThe solvent is composed of alcohol and water in a mass ratio of 1: 1. 0.1mol/L trimesic acid organic ligand solution is prepared, wherein the solvent composition is that the mass ratio of alcohol to water is 2: 1. Blending the prepared europium nitrate solution of metal salt and organic ligand solution of trimesic acid according to the volume ratio of 3:1, then placing the mixture in a water bath shaking table at the temperature of 20 ℃, uniformly shaking the mixture for 12 hours to prepare metal organic framework fibers, placing the metal organic framework fibers in silver nitrate solution for adsorption for 30min, taking out the metal organic framework fibers, performing suction filtration and washing, and then placing the metal organic framework fibers in NaHPO4Reacting for 5h to prepare Eu (BTC) MOFs nano-fiber doped with nano-metal silver particles;
dispersing thermoplastic nano-fibers (polyamide) and the Eu- (BTC) MOFs nano-fibers doped with nano-metallic silver particles in alcohol water to form a suspension (preferably a mixed solution of methanol and water), wherein the Eu- (BTC) MOFs nano-fibers doped with nano-metallic silver particles in the suspension are 1 mass percent, and the Eu- (BTC) MOFs nano-fibers doped with nano-metallic silver particles in the suspension and the thermoplastic nano-fibers are in a mass ratio of 0.1: 1.
The suspension is coated on a base material (woven cloth), and is frozen for 4 hours at the temperature of minus 60 ℃ by a freeze drying technology, and is dried for 24 hours to obtain the nanofiber gel material with the synergistic function of pollutant adsorption, catalysis and fluorescence tracking.
Example 10
Preparing 0.15mol/L europium nitrate solution, wherein the solvent composition is that the mass ratio of alcohol to water is 1: 1. 0.15mol/L trimesic acid organic ligand solution is prepared, wherein the solvent composition is that the mass ratio of alcohol to water is 2: 1. Blending the prepared europium nitrate solution of metal salt and organic ligand solution of trimesic acid according to the volume ratio of 2:1, then placing the mixture in a water bath shaking table at the temperature of 20 ℃, uniformly shaking the mixture for 12 hours to prepare metal organic framework fibers, placing the metal organic framework fibers in silver nitrate solution for adsorption for 30min, taking out the metal organic framework fibers, performing suction filtration and washing, and then placing the metal organic framework fibers in NaHPO4Reacting for 5 hours to prepare Eu (BTC) MOFs nano-fibers with the surfaces and the interiors both doped with nano-metal silver particles;
dispersing thermoplastic nano-fiber (polyamide) and the Eu- (BTC) MOFs nano-fiber doped with nano-metal silver particles in alcohol water to form a suspension (preferably a mixed solution of methanol and water), wherein the Eu- (BTC) MOFs nano-fiber doped with nano-metal silver particles in the interior accounts for 1% by mass, and the Eu- (BTC) MOFs nano-fiber and the thermoplastic nano-fiber both doped with nano-metal silver particles in the interior account for 0.1:1 by mass.
The suspension is coated on a base material (woven cloth), and is frozen for 4 hours at the temperature of 70 ℃ below zero by a freeze-drying technology, and is dried for 24 hours to obtain the nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking.
Example 11
Preparing 0.2mol/L europium nitrate solution, wherein the solvent composition is that the mass ratio of alcohol to water is 1: 1. 0.2mol/L trimesic acid organic ligand solution is prepared, wherein the solvent composition is that the mass ratio of alcohol to water is 2: 1. Blending the prepared metal salt europium nitrate solution and the organic ligand according to the volume ratio of 3:1, then placing the mixture in a water bath shaking table at 20 ℃, uniformly shaking the mixture for 12 hours to prepare metal organic framework fibers, placing the metal organic framework fibers in a silver nitrate solution for adsorption for 30 minutes, taking out the metal organic framework fibers, performing suction filtration and washing, and then placing the metal organic framework fibers in NaHPO4Reacting for 5 hours to prepare Eu (BTC) MOFs nano-fibers with the surfaces and the interiors both doped with nano-metal silver particles;
dispersing thermoplastic nano-fibers (polyamide) and the Eu- (BTC) MOFs nano-fibers doped with nano-metal silver particles in alcohol water to form a suspension (preferably a mixed solution of methanol and water), wherein the Eu- (BTC) MOFs nano-fibers doped with nano-metal silver particles in the suspension are 1 mass percent, and the Eu- (BTC) MOFs nano-fibers doped with nano-metal particles in the suspension and the thermoplastic nano-fibers are in a mass ratio of 0.1: 1.
The suspension is coated on a base material (woven cloth), and is frozen for 4 hours at the temperature of minus 10 ℃ and dried for 24 hours by a freeze-drying technology to obtain the nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking.
Example 12
Preparing 0.3mol/L europium nitrate solution, wherein the solvent composition is that the mass ratio of alcohol to water is 1: 1. Prepared 0.3mol/L trimesic acid organic complexThe solvent of the solution is alcohol-water mass ratio of 2: 1. Blending the prepared europium nitrate solution of metal salt and organic ligand solution of trimesic acid according to the volume ratio of 3:1, then placing the mixture in a water bath shaking table at the temperature of 20 ℃, uniformly shaking the mixture for 12 hours to prepare metal organic framework fibers, placing the metal organic framework fibers in silver nitrate solution for adsorption for 30min, taking out the metal organic framework fibers, performing suction filtration and washing, and then placing the metal organic framework fibers in NaHPO4Reacting for 5 hours to prepare Eu (BTC) MOFs nano-fibers with the surfaces and the interiors both doped with nano-metal silver particles;
dispersing thermoplastic nano-fibers (polyamide) and the Eu- (BTC) MOFs nano-fibers doped with nano-metal silver particles in alcohol water to form a suspension (preferably a mixed solution of methanol and water), wherein the Eu- (BTC) MOFs nano-fibers doped with nano-metal silver particles in the suspension are 1 mass percent, and the Eu- (BTC) MOFs nano-fibers doped with nano-metal particles in the suspension and the thermoplastic nano-fibers are in a mass ratio of 0.1: 1.
The suspension is coated on a base material (woven cloth), and is frozen for 4 hours at the temperature of minus 10 ℃ and dried for 24 hours by a freeze-drying technology to obtain the nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking.
The above examples are merely preferred examples and are not intended to limit the embodiments of the present invention. In addition to the above embodiments, the present invention has other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.

Claims (6)

1. A nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking is characterized in that: the metal organic framework nanofiber is formed by mutually intertwining metal organic framework nanofibers and thermoplastic polymer nanofibers in a three-dimensional space through hydrogen bond acting force, wherein nano metal particles are doped in the metal organic framework nanofibers, and the metal organic framework nanofibers comprise the following components in percentage by mass:
thermoplastic polymer nanofibers: 20 to 99 percent;
metal organic framework nanofiber: 1% -80%;
wherein the fiber diameter of the metal organic framework nanofiber is 20-1000 nm, and the fiber length is 5-100 mu m; the particle size of the nano metal particles is 1-10 nm; the metal organic framework nanofiber is prepared from rare earth metal salt and an organic ligand, wherein the rare earth metal salt is an inorganic compound consisting of at least one element of Eu, Ga, Tb, Sm, Yb or Ru, the organic ligand is polybasic organic carboxylic acid containing a benzene ring structure, and the polybasic organic carboxylic acid containing the benzene ring structure is at least one of trimesic acid, 1,3, 5-tri (4-carboxyphenyl) benzene or nitrilotriacetic acid;
the nano metal particles are at least one of silver, gold, platinum, copper, iron, nickel or palladium;
the thermoplastic polymer nanofiber is a nanofiber with the fiber diameter of 50-500 nm, which is prepared by a thermoplastic polymer through a melt blending phase separation method; the thermoplastic polymer is one of polyamide and ethylene vinyl alcohol copolymer;
and the preparation method of the nanofiber gel material comprises the following steps:
1) preparing metal organic framework nano fibers: uniformly mixing a rare earth metal salt solution and an organic ligand solution to obtain a mixed stock solution, placing the mixed stock solution in a water bath shaking table, uniformly shaking to obtain nano fibers, placing the nano fibers in a precursor salt solution of nano metal particles, continuing the oscillation of the water bath shaking table, performing suction filtration and washing to obtain metal-organic framework nano fibers with nano metal cations adsorbed inside, and performing reduction treatment to obtain the metal-organic framework nano fibers with the nano metal particles doped inside;
2) preparing thermoplastic polymer nanofibers;
3) preparing a suspension: taking the metal organic framework nano fibers obtained in the step 1), and dispersing the thermoplastic polymer nano fibers obtained in the step 2) in a mixed solvent to form a uniform suspension;
4) preparing an aerogel material: coating the suspension obtained in the step 3) on the surface of a base material for storage, and preparing the nanofiber gel material by using a freeze-drying technology.
2. The preparation method of the nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking as claimed in claim 1, is characterized in that: the preparation method comprises the following preparation steps:
1) preparing metal organic framework nano fibers: uniformly mixing a rare earth metal salt solution and an organic ligand solution to obtain a mixed stock solution, placing the mixed stock solution in a water bath shaking table, uniformly shaking to obtain nano fibers, placing the nano fibers in a precursor salt solution of nano metal particles, continuing the oscillation of the water bath shaking table, performing suction filtration and washing to obtain metal-organic framework nano fibers with nano metal cations adsorbed inside, and performing reduction treatment to obtain the metal-organic framework nano fibers with the nano metal particles doped inside;
2) preparing thermoplastic polymer nanofibers;
3) preparing a suspension: taking the metal organic framework nano fibers obtained in the step 1), and dispersing the thermoplastic polymer nano fibers obtained in the step 2) in a mixed solvent to form a uniform suspension;
4) preparing an aerogel material: coating the suspension obtained in the step 3) on the surface of a base material for storage, and preparing the nanofiber gel material by using a freeze-drying technology.
3. The method for preparing the nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking according to claim 2, wherein the method comprises the following steps: in the step 1), the volume ratio of the rare earth metal salt solution to the organic ligand solution is (1-3) to 1, and the water temperature of the water bath shaking table is 20-50 ℃.
4. The method for preparing the nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking according to claim 3, wherein the method comprises the following steps: the rare earth metal salt solution is prepared by dissolving an inorganic compound consisting of at least one element of Eu, Ga, Tb, Sm, Ya or Ru into a mixed solution of an organic solvent and water to obtain a solution with the concentration of 0.01-0.5 mol/L, wherein the volume ratio of the organic solvent to the water is (1-4): 1;
the organic ligand solution is prepared by dissolving at least one of trimesic acid, 1,3, 5-tri (4-carboxyphenyl) benzene or nitrilotriacetic acid in a mixed solution of an organic solvent and water to obtain a solution with the concentration of 0.01-0.5 mol/L, wherein the volume ratio of the organic solvent to the water is (2-8): 1.
5. the method for preparing the nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking according to claim 4, wherein the method comprises the following steps: the organic solvent is one of ethanol, methanol or DMF.
6. The method for preparing nanofiber gel material with the synergistic functions of pollutant adsorption, catalysis and fluorescence tracking according to claim 2, 3, 4 or 5, wherein the method comprises the following steps: in the step 3), the mixed solvent is a mixed solution of water and an organic solvent, and the organic solvent is one of ethanol, methanol or DMF.
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